Process for dyeing anionically modified synthetic fiber materials

ABSTRACT

Exhaustion process for dyeing automatically modified fibre materials with cationic dyestuffs from halogenated hydrocarbons, wherein are used cationic dyestuffs of the formula 
     
         [F - (R).sub.z ]+A- 
    
     in which F, R, z and A- have the meaning given below in the disclosure; by the claimed process an essentially improved exhaustion of the dyebaths is achieved.

This is a division of application, Ser. No. 564,104, filed Apr. 1, 1975, now U.S. Pat. No. 3,980,430 which is a division of Ser. No. 299,658 filed Oct. 24, 1972 now U.S. Pat. No. 3,925,015.

The invention relates to an exhaustion process for dyeing anionically modified synthetic fibre materials with cationic dyestuffs; more particularly it concerns an exhaustion process for dyeing anionically modified synthetic fibre materials with cationic dyestuffs from halogenated hydrocarbons, wherein are used as cationic dyestuffs of the formula

    [F - ( R ).sub.z ] .sup.+  A.sup.-                         (I)

in which

F represents the radical of a dyestuff cation possessing at least one aromatic or hetero-aromatic ring,

R denotes a C₁ -C₁₂ -alkyl, C₃ -C₁₂ -alkoxy or C₅ -C₆ -cycloalkyl group, preferably a C₄ -C₇ -alkyl, C₄ -C₇ -alkoxy or C₅ -C₆ -cycloalkyl group,

z is 1, 2 or 3 and

A⁻ is an anion,

With the proviso that the radical or radicals R are bonded to aromatic and/or hetero-aromatic ring systems of the dyestuff cation and that if R is a C₁ -C₂ -alkyl group, z is 3 and the 3 R are located on one and the same aromatic or hetero-aromatic ring.

As examples of R there may be mentioned: as C₁ -C₁₂ -alkyl radicals, the methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, 2-methylbutyl, pentyl-(2), pentyl-(3), n-hexyl, hexyl-(2), hexyl-(5), n-heptyl, heptyl-(2), heptyl-(3), heptyl-(4), n-octyl, octyl-(2), octyl-(3), octyl-(4), n-nonyl, nonyl-(2), n-decyl, decyl-(2), n-undecyl, undecyl-(2), n-dodecyl and dodecyl-(2) radical; as C₃ -C₁₂ -alkoxy radicals the n-propoxy, i-propoxy, n-butoxy, i-butoxy, tert.butoxy, n-pentoxy, i-pentoxy, n-hexoxy, hexyl-(2)-oxy, n-heptoxy, heptyl-(3)-oxy, n-octyloxy, octyl-(2)-oxy, octyl-(4)-oxy, n-nonyloxy, nonyl-(2)-oxy, n-decyl, decyl-(2)-oxy, n-undecyloxy, undecyl-(2)-oxy, n-dodecyloxy and dodecyl-(2)-oxy radical; and as C₅ -C₆ -cycloalkyl radicals the cyclopentyl and cyclohexyl radical.

Possible anions A⁻ are especially the anions of inorganic or organic acids which are customary for basic dyestuffs. As examples there may be mentioned: as anions of inorganic acids, the chloride, bromide, iodide, carbonate, bicarbonate, sulphate, bisulphate, disulphate, aminosulphonate, phosphate, dihydrogenophosphate, nitrate and perchlorate ion and also ZnCl₃ ⁻ ; as anions of aliphatic and aromatic sulphonic acids or acid sulphuric acid esters such as the methanesulphonate, benzenesulphonate, p-toluenesulphonate, p-chlorobenzenesulphonate, methylsulphate and ethylsulphate ion, and as anions of organic acids the anion of formic acid, acetic acid, chloroacetic acid, propionic acid, lactic acid, crotonic acid, benzoic acid, oxalic acid, malonic acid, maleic acid, citric acid, tartaric acid, succinic acid, adipic acid and suberic acid.

Dyestuffs of the formula I in which the radical R contains 4 to 7 C atoms, for example dyestuffs which contain one to three tert.-butyl or heptyl-(3) radicals, are preferred.

Dyestuffs which have proved particularly valuable are those of the formula I wherein the dyestuff cation

    [F - ( R ).sub.z ] .sup.+

is

A. a dyestuff cation of the formula ##STR1## in which R₁ denotes hydrogen, alkyl, cycloalkyl, aralkyl or aryl,

R₂ denotes C₁ -C₅ -alkyl, cycloalkyl or aralkyl,

R₃ denotes C₁ -C₅ -alkyl, cycloalkyl or aralkyl,

R₄ denotes halogen, alkyl, cycloalkyl, aralkyl, alkoxy, nitro, carbalkoxy, nitrile, acyl, acylamino, amino, carbamoyl, N-alkyl-carbamoyl, N,N-dialkylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulphamoyl, N-alkylsulphamoyl,

N,n-dialkylsulphamoyl, alkylsulphonyl, arylsulphonyl, trifluoromethyl, aryloxy, aralkoxy or carbaralkoxy,

y represents --CH= or --N= and

G represents the radicals ##STR2## in which R'₁ denotes hydrogen, alkyl, cycloalkyl, aralkyl or aryl,

R'₂ denotes C₁ -C₅ -alkyl, cycloalkyl or aralkyl,

R'₃ denotes C₁ -C₅ -alkyl, cycloalkyl or aralkyl,

R'₄ denotes halogen, alkyl, cycloalkyl, aralkyl, alkoxy, nitro, carbalkoxy, nitrile, acyl, acylamino, amino, carbamoyl, N-alkyl-carbamoyl, N,N-dialkylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl, alkylsulphonyl, arylsulphonyl, trifluoromethyl, aryloxy, aralkoxy or carbaralkoxy,

R₅ represents halogen, alkyl, cycloalkyl, aralkyl, alkoxy, nitro, carbalkoxy, nitrile, acyl, acylamino, amino, carbamoyl, N-alkyl-carbamoyl, N,N-dialkylcarbamoyl, N-alkyl-N-arylcarbamoyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl, alkylsulphonyl, arylsulphonyl, trifluoromethyl, aryloxy, aralkoxy or carbaralkoxy,

R₆ denotes hydrogen; a lower alkyl which is optionally substituted, for example by C₁ -C₅ -carbalkoxy or C₁ -C₅ -alkoxy; an alkyl radical which in the o-position of the ring B, if a = o, can close a 5-membered or 6-membered ring, the heterocyclic ring thereby formed being optionally alkyl-substituted or condensed with a further carbocyclic ring; cycloalkyl, aralkyl or C₁ -C₅ -alkenyl;

R₇ is hydrogen; alkyl, which can optionally close a 5-membered or 6-membered ring to the adjacent o-position of the ring B, the heterocyclic ring thereby formed being optionally alkyl-substituted or fused to a further carbocyclic ring; cycloalkyl; aralkyl or aryl;

R₈ hydrogen, alkyl or aralkyl; R₇ and R₈ can further, with the nitrogen atom, close a heterocyclic ring which can optionally contain further hetero-atoms;

R₉ hydrogen, alkyl, alkoxy or halogen,

R₁₀ hydrogen, alkyl, aralkyl, cycloalkyl or aryl,

R₁₁ alkyl, aryl, carboxylic acid ester or an optionally substituted carbonamide group;

R₁₈ hydrogen, nitrile, carboxylic ester or carbonamide,

X represents --CH₂ -- or O,

a represents the numbers 0 or 1 and

m, n and p independently of one another represent a number from 0 to 3,

with the proviso that at least one of the substituents R₄, R₄ ', R₅, R₉ or R₁₁ is a C₃ -C₁₂ -alkyl, C₃ -C₁₂ -alkoxy or C₅ -C₆ -cycloalkyl group or R₁₀ is a C₃ -C₁₂ -alkyl or C₅ -C₆ -cycloalkyl group or R₄, R₄ ' or R₅ is a C₁ -C₂ -alkyl group, in which case n, p or m have the value 3.

Dyestuffs of the formula II in which R₄ represent a t-butyl group in the 5-position and/or R₅ represents a t-butyl group in the p-position and/or R₉ represents a t-butyl group in the 5-position are particularly preferred.

B. A dyestuff cation of the formula ##STR3## in which R₁₂ represents hydrogen, alkyl, aralkyl, cycloalkyl or aryl,

R₁₃ represents hydrogen, alkyl, cycloalkyl or aralkyl, or R₁₂ and R₁₃ together with the nitrogen atom form a heterocyclic ring which can optionally contain further hetero-atoms,

R₁₄ can represent hydrogen, halogen, alkoxy, aralkoxy, aryloxy, acyloxy, alkyl, aralkyl, aryl, nitro, nitrile, trifluoromethyl, carboxylic acid ester, optionally N-substituted carbonamide groups, acyl, alkylsulphonyl or arylsulphonyl or ##STR4## with R₁₅ and R₁₆ having the meaning given below, and K represents the radicals ##STR5## in which R₉, R₁₀ and R₁₁ have the abovementioned meanings;

R₁₅ represents hydrogen, alkyl, cycloalkyl or aralkyl;

R₁₆ represents hydrogen, alkyl, aralkyl, cycloalkyl or aryl or

R₁₅ and R₁₆, together with the nitrogen atom, form a heterocyclic ring which can optionally contain further hetero-atoms; and

R₁₇ denotes hydrogen, halogen, alkyl or alkoxy, with the proviso that at least one of the substituents R₉,

R₁₁, r₁₄ or R₁₇ is a C₃ -C₁₂ -alkyl, C₃ C₁₂ -alkoxy or C₅ -C₆ -cycloalkyl group or R₁₀ is a C₃ -C₁₂ -alkyl or C₅ -C₆ -cycloalkyl group.

Dyestuffs of the formula III in which either R₁₄ represents a tert. butyl group in the p-position and/or R₉ represents a tert. butyl group in the 5-position are particularly preferred.

The aromatic carbocyclic rings of the dyestuff cations II and III can be fused to carbocyclic rings and can also contain, additionally to the substituents R₄, R₄ ' , R₅, R₉, R₁₄ and R₁₇, further non-ionic substituents such as fluorine, chlorine or bromine atoms and also methyl, ethyl, methoxy, carbomethoxy, nitro and nitrile groups.

The aryloxy, aralkoxy, carbaralkoxy and aralkyl radicals can be substituted in the aromatic radical, especially by lower alkyl, halogen, such as fluorine, chlorine or bromine, alkoxy, carboalkoxy, nitrile, nitro and/or hydroxyl.

As examples of the groups or radicals named in the definitions, there may be mentioned:

As lower alkyl groups: C₁ -C₅ -alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, i-butyl, t-butyl an iso-amyl.

As alkyl groups: C₁ -C₁₂ -alkyl groups, such as have been listed for R, and also lower substituted alkyl radicals such as the 2-cyanoethyl, 2-chloroethyl and 2-hydroxyethyl radical;

Alkoxy represents methoxy, ethoxy or larger alkoxy radicals, such as are described for the radical R;

Carbalkoxy in particular represents carbomethoxy, carboethoxy, carbopropoxy and carbobutoxy;

Acyl radicals are especially the acetyl, propionyl, benzoyl and toluyl radical;

Suitable acylamino radicals are, for example, the formylamino, acetylamino, n-propionylamino, benzoylamino, 4-chlorobenzoylamino and 4-methylbenzoylamino radical.

As examples or aralkyl radicals there may be mentioned: the benzyl, β-phenylethyl and α,α-dimethylbenzyl radical as well as their derivatives substituted in the phenyl nucleus.

As cycloalkyl, cyclohexyl is of particular importance.

Aryl represents carbocyclic aromatics with 6-10 carbon atoms such as phenyl and naphthyl and their derivatives such as 4-methylphenyl, 2-methylphenyl, 4-chlorophenyl, 2-chlorophenyl and 2-methyl-4-chloro-phenyl.

N-alkyl-carbamoyl and N,N-dialkyl-carbamoyl represent, for example, methyl-carbamoyl, N-ethyl-carbamoyl, N-n-butyl-carbamoyl, N,N-dimethyl-carbamoyl, N,N-diethyl-carbamoyl and N-methyl-N-ethyl-carbamoyl.

N-alkyl-N-aryl-carbamoyl represents, for example, N-methyl-N-phenyl-carbamoyl and N-ethyl-N-phenyl-carbamoyl.

N-alkyl-sulphamoyl and N,N-dialkyl-sulphamoyl represent, for example, N-methyl-sulphamoyl, N-ethyl-sulphamoyl, N,N-dimethyl-sulphamoyl and N,N-diethyl-sulphamoyl.

As aryloxy radicals there should be mentioned, for example: the phenoxy and naphthoxy radical and their derivatives which are substituted in the aromatic ring.

Suitable aralkoxy radicals are, for example, benzyloxy, phenylethoxy, α,α-dimethylbenzyloxy and their derivatives which are optionally substituted in the phenyl nucleus. Carbaralkoxy radicals are, for example, carbobenzoxy, carbo-α-phenylethoxy, carbo-(β-phenylethoxy) and carbo-(γ-phenyl-n-propoxy) radicals and their derivatives substituted in the phenyl nucleus.

The dyestuffs to be used according to the invention are manufactured in accordance with processes which are in themselves known. These are described, for example, in German Patent Specifications Nos. 686,198 and 742,039 or British Pat. Nos. 840,282, 875,995 or 1,139,407, The dyestuffs which according to the invention, are added to the halogenated hydrocarbon dye baths can vary within wide limits depending on the desired depth of colour; in general, amounts of 0.1-8 percent by weight, relative to the weight of the material to be dyed which is employed, have proved successful.

It has proved advantageous to add to the halogenated hydrocarbon dyeing liquors small amounts, for example 0.1-4, preferably 0.1-2, % by weight of water, relative to the weight of the halogenated hydrocarbon. At the same time it has proved advantageous also to add to the halogenated hydrocarbon solutions, for distillation of the water, emulsifiers in an amount of 0.1-2% by weight relative to the weight of the halogenated hydrocarbon. Possible emulsifiers are preferably non-ionic compounds; oxethylation products of fatty alcohols, phenols, fatty acid amides and fatty acids, as well as their mixtures, have proved successful.

The anionically modified synthetic fibre materials to be dyed according to the invention are in particular polyacrylonitrile modified by carboxyl and/or sulphonic acid groups, polyesters modified by carboxyl and/or sulphonic acid groups, such as polyethylene terephthalate, polycyclohexanedimethylene terephthalate, heterogeneous polyesters of terephthalic acid, isophthalic acid and ethylene glycol or of terephthalic acid, sulphoisophthalic acid and ethylene glycol, and also copolyether-ester fibres from p-hydroxybenzoic acid, terephthalic acid and ethylene glycol, or polyamides such as polyhexamethylene adipate, polycaprolactam or poly-ω-aminoundecanoic acid, modified by sulphonic acid groups. These anionically modified, synthetic fibre materials can, during dyeing, also be present as a mixture with unmodified synthetic fibre materials. The unmodified fibre component is not dyed by the cationic dyestuffs and can subsequently be dyed with another non-cationic dyestuff.

Dyeing of the anionically modified, synthetic fibre materials from chlorinated hydrocarbon solutions, which is preferably effected in closed apparatuses, can take place, for example, by introducing the fibre materials, at room temperature, into the chlorinated hydrocarbon dyeing liquors which contain the cationic dyestuffs and advantageously small amounts of water, as well as the optionally used emulsifiers, heating the bath to temperatures of 70°-140° C. and keeping it at this temperature until the liquor is exhausted. After cooling, the liquor is separated off. The fibre materials are optionally briefly rinsed with fresh solvent, and are freed of the adhering solvent by suction filtration or centrifugation and subsequent drying in a stream of air.

Using the process according to the invention, it proves possible to dye anionically modified, synthetic fibre materials, in the most diverse states of processing, for example as flocks, tows, yarn, piece goods, pile fabrics or made-up goods, by means of cationic dyestuffs from chlorinated hydrocarbon solutions, to give deep shades of excellent evenness. The dyeings obtained have very good rub resistance. The exhaustion of the bath is very good in the process according to the invention.

Halogenated hydrocarbons which can be used for the process according to the invention are those of boiling point between 40° and 170° C., especially aliphatic chlorinated hydrocarbons, such as methylene chloride, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, 1-chloropropane, 2-chloropropane, 1,2-dichloropropane, 1-chlorobutane, 2-chlorobutane, 1,4-dichlorobutane, 1-chloro-2-methylpropane or 2-chloro-2-methylpropane as well as aliphatic fluoro- and fluoro-chloro-hydrocarbons, such as perfluoro-n-hexane, 1,2,2-trifluorotrichloroethane and trifluoropentachloropropane and aromatic chlorinated hydrocarbons and fluorinated hydrocarbons, such as chlorobenzene, fluorobenzene, chlorotoluene and benzotrifluoride.

Tetrachloroethylene, trichloroethylene and 1,1,1-trichloropropane have been proved particularly successful.

The cationic dyestuffs of the formula I to be used according to the invention are distinguished by good solubility in halogenated hydrocarbons, for example tetrachloroethylene.

An exhaustion process for dyeing synthetic fibre materials, containing anionic groups, by means of cationic dyestuffs from halogenated hydrocarbons is already known from British Pat. No. 1,234,727.

The process according to the invention differs from this process in that in it cationic dyestuffs are used which possess a dyestuff cation which is soluble in chlorinated hydrocarbons, whilst according to the process of the German Offenlegungsschrift (German Published Specification) cationic dyestuffs are used which are rendered soluble in chlorinated hydrocarbon by the introduction of a lipophilic anion.

This difference in the conversion of water soluble cationic dyestuffs into cationic dyestuffs which are soluble in chlorinated hydrocarbons is very important technologically.

Using the cationic dyestuffs to be employed according to the invention, better bath exhaustion is achieved, because of the absence of retarding anions, than with the dyestuffs described in British Pat. No. 1,234,727. As a result, no difficulties in levelling occur when dyeing with combinations of different cationic dyestuffs of the formula I such as is often the case when dyeing with the cationic dyestuffs described in the British Patent.

With the aid of the dyestuffs to be used according to the invention, level, reproducible dyeings are obtained in a simple manner even when dyeing with dyestuff combinations.

The parts indicated in the examples which follow are parts by weight, unless otherwise stated.

EXAMPLE 1

Fibre yarn of anionically modified polyacrylonitrile is introduced, in a liquor ratio of 1:10, into a dye bath which per liter of tetrachloroethylene contains 1 g of the dyestuff of the formula ##STR6## 1 g of oleic acid ethanolamide, 1 g of the reaction product of 1 mol of oleyl alcohol with 20 mols of ethylene oxide, 8 g of water and 1 g of glacial acetic acid. The dye bath is heated in a closed dyeing machine to 100° C. for 60 minutes, with vigorous agitation of the liquor. Thereafter the yarn is rinsed with fresh solvent and dried. A golden yellow dyeing of excellent fastness properties is obtained.

The dyestuff employed had been manufactured as follows: 5.2 parts of p-anisidine in 100 parts of water were diazotised, in the presence of 15.5 parts of 30% strength hydrochloric acid, with a solution of 2.95 parts of sodium nitrite in 15 parts by volume of water. After destroying the excess nitrite with amidosulfphonic acid, 9.7 parts of 1,3,3 trimethyl-2-methylene-5-tertiary butyl-2,3-dihydroindole were added at 5° C. A solution of 12.5 parts of sodium acetate trihydrate in 50 parts of water was then added dropwise over the course of 1 hour. After the temperature had risen to 20° C., the resulting dyestuff was salted out. After being filtered off, it was stirred into a mixture of 200 parts by volume of chlorobenzene and 100 parts of water at 80° C., whilst at the same time keeping the pH value of the aqueous layer at pH 9-10 by adding sodium hydroxide solution. After stirring for a further 15 minutes, the organic layer was separated off, 1.7 parts of triisopropanolamine were added and the dehydration was effected by distilling off about 30 parts by volume of liquid at approx. 80° C. under reduced pressure. 7 parts of dimethyl sulphate were then added dropwise at 80° C. and the mixture was further stirred until the methylation was complete. After stripping off the chlorobenzene in steam, the dyestuff was isolated by salting out with sodium chloride from the aqueous distillation residue.

Equivalent dyeings, in the colour shades indicated in the table, were also obtained if instead of the dyestuff used the same amount of one of the dyestuffs obtained in the reaction of the dihydroindoles and anilines indicated in the table, under the manufacturing conditions described for the dyestuff used, was employed.

                                      Table                                        __________________________________________________________________________     Dihydroindole                       Aniline           Colour                   __________________________________________________________________________                                                           Shade                    1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                   p-tertiary-Butylaniline                                                                             yellow                   1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                   2,4,5-Trimethylaniline                                                                              yellow                   1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                   p-i-Butoxyaniline    golden                                                                         yellow                   1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                   p-n-Butoxyaniline    golden                                                                         yellow                   1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                   p-(2-Methyl-butoxy)- golden                                                    aniline              yellow                   1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                   p-Heptyl (3)-oxy-aniline                                                                            golden                                                                         yellow                   1,3,3-Trimethyl-2-methylene-2,3-dihydroindole                                                                   p-Hexyloxy-aniline   golden                                                                         yellow                   1,3,3-Trimethyl-2-methylene-5-tertiary-butyl-2,3-dihydro-                                                       p-i-Propoxyaniline   golden                   indole                                                yellow                   1,3,3-Trimethyl-2-methylene-5-tertiary-butyl-2,3-dihydro-                                                       p-Benzyloxyaniline   golden                   indole                                                yellow                   1,3,3-Trimethyl-2-methylene-5-tertiary-butyl-2,3-dihydro-                                                       p-tertiary-Butylaniline                                                                             yellow                   indole                                                                         1,3,3-Trimethyl-2-methylene-5-tertiary-butyl-2,3-dihydro-                                                       4-Aminodiphenyl-ether                                                                               golden                   indole                                                yellow                   1,3,3-Trimethyl-7-phenoxy-2-methylene-2,3-dihydroindole                                                         tert.-Butylaniline   golden                                                                         yellow                   1,3,3-Trimethyl-5-phenoxy-2-methylene-2,3-dihydroindole                                                         tert.-Butylaniline   golden                                                                         yellow                   1,3,3-Trimethyl-7-benzyloxy-2-methylene-2,3-dihydroindole                                                       tert.-Butylaniline   golden                                                                         yellow                   1,3,3-Trimethyl-5-n-butoxy-2-methylene-2,3-dihydroindole                                                        p-Anisidine          golden yellow            1,3,3-Trimethyl-5-n-butoxy-2-methylene-2,3-dihydroindole                                                        p-Toluidine          golden yellow            1,3,3-Trimethyl-5-methyl-2-methylene-2,3-dihydroindole                                                          4-tertiary-Butylaniline                                                                             reddish-tinged                                                                 yellow                   1,3,3-Trimethyl-5-methoxy-2-methylene-2,3-dihydroindole                                                         4-tertiary-Butylaniline                                                                             golden-yellow            1,3,3-Trimethyl-5-carbomethoxy-2-methylene-2,3-dihydro-                                                         4-tertiary-Butylaniline                                                                             golden yellow            indole                                                                         1,3,3-Trimethyl-5-carboethoxy-2-methylene-2,3-dihydro-                                                          4-tertiary-Butylaniline                                                                             golden yellow            indole                                                                         1,3,3-Trimethyl-5-cyclohexyl-2-methylene-2,3-dihydro-                                                           4-tertiary-Butylaniline                                                                             golden yellow            indole                                                                         1,3,3-Trimethyl-5-benzyl-2-methylene-2,3-dihydroindole                                                          4-tertiary-Butylaniline                                                                             reddish-tinged                                                                 yellow                   1,3,3-Trimethyl-5-nitro-2-methylene-2,3-dihydroindole                                                           4-tertiary-Butylaniline                                                                             yellowish                                                                      tinged orange            1,3,3-Trimethyl-7-methyl-2-methylene-2,3-dihydroindole                                                          4-tertiary-Butylaniline                                                                             reddish-tinged                                                                 yellow                   1,3,3-Trimethyl-5-trifluoromethyl-2-methylene-2,3-                                                              4-tertiary Butylaniline                                                                             reddish-tinged           dihydroindole                                         yellow                   1,3,3-Trimethyl-7-methoxy-2-methylene-2,3-dihydroindole                                                         4-tertiary-Butylaniline                                                                             reddish-tinged                                                                 yellow                   1,3,3-Trimethyl-7-chloro-2-methylene-2,3-dihydroindole                                                          4-tertiary-Butylaniline                                                                             reddish-tinged                                                                 yellow                   1,3,3-Trimethyl-5-chloro-2-methylene-2,3-dihydroindole                                                          4-tertiary-Butylaniline                                                                             golden yellow            1-Ethyl-3,3-dimethyl-2-methylene-2,3-dihydroindole                                                              4-tertiary-Butylaniline                                                                             reddish-tinged                                                                 yellow                   1-Ethyl-3,3-dimethyl-5-methyl-2-methylene-2,3-dihydro-                                                          4-tertiary-Butylaniline                                                                             reddish-tinged           indole                                                yellow                   1-Ethyl-3,3-dimethyl-5-chloro-2-methylene-2,3-dihydroindole                                                     4-tertiary-Butylaniline                                                                             golden yellow            1-Ethyl-3,3-dimethyl-5-methoxy-2-methylene-2,3-dihydroindole                                                    4-tertiary-Butylaniline                                                                             golden yellow            1-Ethyl-3,3-dimethyl-5-carboethoxy-2-methylene-2,3-dihydro-                                                     4-tertiary-Butylaniline                                                                             golden yellow            indole                                                                         1-Ethyl-3,3-dimethyl-5-cyclohexyl-2-methylene-2,3-dihydro-                                                      4-tertiary-Butylaniline                                                                             golden yellow            indole                                                                         1-Ethyl-3,3-dimethyl-5-benzyl-2-methylene-2,3-dihydroindole                                                     4-tertiary-Butylaniline                                                                             golden yellow            1-Ethyl-3,3-dimethyl-5-nitro-2-methylene-2,3-dihydroindole                                                      4-tertiary-Butylaniline                                                                             yellowish-                                                                     tinged orange            1,3,3-Trimethyl-7-benzyl-2-methylene-2,3-dihydroindole                                                          4-tertiary-Butylaniline                                                                             reddish-                                                                       tinged yellow            Mixture of: 1,3,3-Trimethyl-4-methyl-2-methylene-2,3-di-                                                        4-tertiary-Butylaniline                                                                             reddish-                 hydroindole and 1,3,3-trimethyl-6-methyl-2-methylene-2,3-                                                                            tinged yellow            dihydroindole                                                                  1,3,3-Trimethyl-6,7-benzo-2-methylene-2,3,3',4',5',6'-                                                          4-tertiary-Butylaniline                                                                             yellowish-               hexahydroindole                                       tinged orange            1,3,3-Trimethyl-5-fluoro-2-methylene-2,3-dihydroindole                                                          4-tertiary-Butylaniline                                                                             golden yellow            1,3,3-Trimethyl-5-ethoxy-2-methylene-2,3-dihydroindole                                                          4-tertiary-Butylaniline                                                                             golden yellow            1,3,3-Trimethyl-7-ethoxy-2-methylene-2,3-dihydroindole                                                          4-tertiary-Butylaniline                                                                             golden yellow            1,3,3-Trimethyl-5-cyano-2-methylene-2,3-dihydroindole                                                           4-tertiary-Butylaniline                                                                             golden yellow            1,3,3-Trimethyl-5-acetylamino-2-methylene-2,3-dihydro-                                                          4-tertiary-Butylaniline                                                                             golden yellow            indole                                                                         1,3,3-Trimethyl-5-methylsulphonyl-2-methylene-2,3-dihydro-                                                      4-tertiary-Butylaniline                                                                             golden yellow            indole                                                                         1,3,3-Trimethyl-5-phenylsulphonyl-2-methylene-2,3-dihydro-                                                      4-tertiary-Butylaniline                                                                             golden yellow            indole                                                                         1,3-Dimethyl-3-ethyl-2-methylene-2,3-dihydroindole                                                              4-tertiary-Butylaniline                                                                             golden yellow            1,3,3-Trimethyl-6,7-benzo-2-methylene-2,3-dihydroindole                                                         4-tertiary-Butylaniline                                                                             yellowish-                                                                     tinged orange            1,3,3-Trimethyl-5-sulphonamido-2-methylene-2,3-dihydroindole                                                    4-tertiary-Butylaniline                                                                             golden yellow            1,3,3-Trimethyl-5-carboamido-2-methylene-2,3-dihydroindole                                                      4-tertiary-Butylaniline                                                                             golden yellow            1,3,3-Trimethyl-5-carboxylic acid ethylanilide-2-methylene-                                                     4-tertiary-Butylaniline                                                                             golden yellow            2,3-dihydroindole                                                              1,3,3-Trimethyl-7-ethyl-2-methylene-2,3-dihydroindole                                                           4-tertiary-Butylaniline                                                                             reddish-                                                                       tinged yellow            1,3,3-Trimethyl-5-chloro-7-methoxy-2-methylene-2,3-dihydro-                                                     4-tertiary-Butylaniline                                                                             golden yellow            indole                                                                         1,3,3-Trimethyl-4-chloro-7-methoxy-2-methylene-2,3-dihydro-                                                     4-tertiary-Butylaniline                                                                             golden yellow            indole                                                                         1,3,3-Trimethyl-4,6-dicarbomethoxy-2-methylene-2,3-dihydro-                                                     4-tertiary-Butylaniline                                                                             golden yellow            indole                                                                         1,3,3-Trimethyl-4,5-dichloro-7-methoxy-2-methylene-2,3-di-                                                      4-tertiary-Butylaniline                                                                             golden yellow            hydroindole                                                                    1,3,3-Trimethyl-5-chloro-4,7-dimethoxy-2-methylene-2,3-di-                                                      4-tertiary-Butylaniline                                                                             golden yellow            hydroindole                                                                    1,3,3,4,5,7-Hexamethyl-2-methylene-2,3-dihydroindole                                                            4-tertiary-Butylaniline                                                                             reddish-                                                                       tinged yellow            1,3,3,4,6,7-Hexamethyl-2-methylene-2,3-dihydroindole                                                            4-tertiary-Butylaniline                                                                             reddish-                                                                       tinged yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydro-                                                       4-Amino-4'-methyl-di-                                                                               golden yellow            indole                           phenyl-ether                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydro-                                                       4-Amino-4'-ethyl-diphenyl                                                                           golden yellow            indole                           ether                                         1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydro-                                                       4-Amino-4'-tert.-butyl-                                                                             golden yellow            indole                           diphenyl-ether                                1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                   4-Amino-4'-cyclohexyl-diphenyl-ether                                                                golden yellow            2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                   4-Amino-2'-methyl-diphenyl-ether                                                                    golden yellow            2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                   4-Amino-3'-methyl-diphenyl-ether                                                                    golden yellow            2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                   4-Amino-4'-methoxy-diphenyl-ether                                                                   golden yellow            2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                               4-Amino-3'-methoxy-diphenyl-ether                                                                   golden yellow            dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                   4-Amino-4'-ethoxy-diphenyl-ether                                                                    golden yellow            2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                               4-Aminophenyl-α-naphthyl-ether                                                                golden yellow            dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                               4-Aminophenyl-β-naphthyl-ether                                                                 golden yellow            dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                               4-Amino-2',3',5'-trimethyl-ether                                                                    golden yellow            dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                               4-Aminodiphenylmethane                                                                              golden yellow            dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                               Aniline              reddish-                 dihydroindole                                         tinged yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                               p-Toluidine          reddish-                 dihydroindole                                         tinged yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                               m-Toluidine          reddish-                 dihydroindole                                         tinged yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                               o-Anisidine          yellow                   dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-                                                               o-Phenetidine        yellow                   dihydroindole                                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  p-Phenetidine        golden yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  4-Aminoacetanilide   golden yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  N-Benzoyl-p-phenylene-                                                                              golden yellow                                             diamine                                       1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  2,4-Dimethoxyaniline golden yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  2,5-Dimethoxyaniline golden yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  3,4-Dimethoxyaniline orange                   1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  2-Chloro-4-aminoanisole                                                                             golden yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  2,4,5-Trimethylaniline                                                                              reddish-                                                                       tinged yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  2,3,5-Trimethylaniline                                                                              reddish-                                                                       tinged yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  5-Amino-2-acetylamino                                                                               orange                                                    anisole                                       1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  6-Amino-3-methoxy-   golden yellow                                             toluene                                       1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  3,4-Dicyanoaniline   golden yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  p-Sulphanilic acid   golden yellow                                             amide                                         1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  4-Aminobenzamide     golden yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  4-Chloroaniline      golden yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  4-Fluoroaniline      golden yellow            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  1,2,3,4-Tetrahydro-5-                                                                               golden yellow                                             aminonaphthalene                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-2,3-dihydroindole                                                  4-Amino-2,5-diethoxy-                                                                               orange                                                    benzoic acid anilide                          1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                   4-Amino-2-methyl-5-methoxybenzanilide                                                               yellowish-               2,3-dihydroindole                                     tinged orange            1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                   4-Cyclohexylaniline  golden yellow            2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                   2,4-Diethoxyaniline  golden yellow            2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                   2-Aminonaphthalene   golden yellow            2,3-dihydroindole                                                              1,3,3-Trimethyl-5-tertiary-butyl-2-methylene-                                                                   3,4-Diisopropoxyaniline                                                                             golden yellow            2,3-dihydroindole                                                              __________________________________________________________________________

EXAMPLE 2

A fabric of anionically modified polyamide is dyed, in accordance with the procedure indicated in Example 1, in a bath which per liter of tetrachloroethylene contains 1 g of the dyestuff of the formula ##STR7## 1 g of oleic acid ethanolamide, 1 g of the reaction product of 1 mol of oleyl alcohol with 20 mols of ethylene oxide, 8 g of water and 1 g of glacial acetic acid.

A level greenish-tinged yellow dyeing of good fastness properties is obtained.

The dyestuff had been manufactured as follows: 10 parts of 1,3,3-trimethyl-5-tertiary butyl-2-methylene-2,3-dihydroindol-ω-aldehyde and 7.8 parts of p-benzyloxyaniline were stirred with 15 parts by volume of glacial acetic acid and 5 parts of water for 4 hours at room temperature. The solution was subsequently diluted with 300 parts of water. After salting out with 20 parts by weight of sodium chloride, the dyestuff was separated from the solution.

Equivalent dyeings, in the colour shades indicated in the table, on the substrates indicated in the table were also obtained if instead of the dyestuff used the same amount of one of the dyestuffs obtained on reaction of the aldehydes and amines indicated in the table, under the manufacturing conditions described for the dyestuff used, was employed. (PA = anionically modified polyacrylonitrile, PE anionically modified polyester).

                                      Table                                        __________________________________________________________________________     Aldehyde                  Amine           Colour Shade                                                                            Substrate                   __________________________________________________________________________     1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-tert.-Butylaniline                                                                           greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   4(p-tert.Butyl)-phen-                                                                          yellow      PE                          hydroindol-ω-aldehyde                                                                           oxyaniline                                              1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-Dodecyloxyaniline                                                                            yellow      PE                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-Cyclohexylaniline                                                                            greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-5-benzyloxy-2-methylene-                                                              p-tert.Butylaniline                                                                            greenish-tinged yellow                                                                     PA                          2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   2-Methyl-2,3-dihydro-                                                                          greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                                           indole                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   p-Anisidine     greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                                           indole                                                  1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   p-tert.-Butylaniline                                                                           greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                                           indole                                                  1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-i-Propoxyaniline                                                                             greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-n-Butoxyaniline                                                                              greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-i-Butoxyaniline                                                                              greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   4-t-Butoxyaniline                                                                              greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-(2-Methylbutoxy                                                                              greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                                           aniline                                                 1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-n-Pentyloxy-aniline                                                                          greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-n-Hexyloxy-aniline                                                                           greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-[Hexyl-(2)-aniline                                                                           greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-n-Heptyloxy-aniline                                                                          greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-n-Octyloxy-aniline                                                                           yellow      PE                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-n-Nonyloxy-aniline                                                                           yellow      PE                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-n-Decyl-oxy-aniline                                                                          yellow      PE                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-n-Undecyloxyaniline                                                                          yellow      PE                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-[Heptyl-(3)-oxy]-aniline                                                                     greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-5-n-butoxy-2-methyl-                                                                  p-Anisidine     greenish-tinged yellow                                                                     PA                          lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-5-n-butoxy-2-methyl-                                                                  2-Methyl-2,3-dihydroindole                                                                     greenish-tinged yellow                                                                     PA                          lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-[Pentyl-(2)-oxy]-aniline                                                                     greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   p-[Hexyl-(2)-oxy]-aniline                                                                      greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   2,3,3-Trimethyl-5-tert.-                                                                       greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                                           butyl-indoline                                          1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   2,3,3-Trimethyl-5-n-butoxy                                                                     greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                                           indoline                                                1,3,3-Trimethyl-2-methylene-t-tert.-                                                                  2,3,3-Trimethyl-5-methoxy                                                                      greenish-tinged yellow                                                                     PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               indoline                                                1,3,3-Trimethyl-2-methylene-5-tert,-                                                                  2,3,3-Trimethyl-5-benzyloxy                                                                    greenish-tinged yellow                                                                     PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               indoline                                                1,3,3-Trimethyl-2-methylene-5.-tert.-                                                                 2,3,3-Trimethyl-5-phenoxy                                                                      greenish-tinged yellow                                                                     PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               indoline                                                1,3,3-Trimethyl-2-methylene-5-tert,-                                                                  2,3,3-Trimethyl-7-phenoxy                                                                      greenish-tinged yellow                                                                     PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               indoline                                                1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   Aniline         greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   p-Toluidine     greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   m-Toluidine     greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   o-Anisidine     yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   m-Anisidine     greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   o-Phenetidine   yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   m-Phenetidine   greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   4-Aminoacetanilide                                                                             greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   N-Benzoyl-p-phenylenediamine                                                                   greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   2,4-Dimethoxyaniline                                                                           reddish-tinged yellow                                                                      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   2,5-Dimethoxyaniline                                                                           reddish-tinged yellow                                                                      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   3,4-Dimethoxyaniline                                                                           reddish-tinged yellow                                                                      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   3,4-Diisopropoxyaniline                                                                        reddish-tinged yellow                                                                      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   2-Chloro-4-aminoanisole                                                                        yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   2,4,5-Trimethylaniline                                                                         greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   2,3,5-Trimethylaniline                                                                         greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   5-Amino-2-acetylamino-                                                                         reddish-tinged yellow                                                                      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                                           anisole                                                 1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   6-Amino-2-methoxy-toluene                                                                      yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                                           anisole                                                 1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   3,4-Dicyanoaniline                                                                             yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   p-Sulphanilic acid amide                                                                       yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   4-Amino-benzamide                                                                              yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   4-Chloroaniline greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   4-Fluoroaniline greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   1,2,3,4-Tetrahydro-5-                                                                          yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                                           amino-naphthalene                                       1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   4-Amino-2,5-diethoxy-N-                                                                        yellowish-tinged                                                                           PAange                      methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   4-Amino-2-methyl-5-                                                                            yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                                           methoxy-N-benzoylaniline                                1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   4-Cyclohexylaniline                                                                            greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   2,5-Diethoxyaniline                                                                            yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   2-Amino-naphthalene                                                                            yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   1,2,3,4-Tetrahydroquinoline                                                                    greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   Hexahydrocarbazole                                                                             yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   1,2,3,4-Tetrahydro-6-                                                                          yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                                           methoxy-quinoline                                       1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   4-Aminodiphenylmethane                                                                         greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω -1,3,3-Trimethyl-5-tertiary-butyl-2-                               4-Amino-4'-methyldiphenyl-                                                                     greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                                           methane                                                 1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   4-Aminodiphenyl-ether                                                                          greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   2-Aminodiphenyl-ether                                                                          greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   4-Amino-4'-methyl-diphenyl-                                                                    greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                                           ether                                                   1,3,3-Trimethyl-5-tertiary-butyl-2-                                                                   4-Amino-4'-ethyl-diphenyl-                                                                     greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                                           ether                                                   1,3,3-Trimethyl-2-methylene-2,3-di-                                                                   4-Amino-4'-tertiary-butyl-                                                                     greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                                           diphenyl-ether                                          1,3,3-Trimethyl-5-methyl-2-methylene-                                                                 p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-methoxy-2-methylene-                                                                p-tertiary-Butylaniline                                                                        yellow      PA                          2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-carbomethoxy-3-methy-                                                               p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimthyl-5-carboethoxy-2-methy-                                                                 p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-5-cyclohexyl-2-methylene-                                                             p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-benzyl-2-methylene-2,3-                                                             p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-5-nitro-2-methylene-2,3-                                                              p-tertiary-Butylaniline                                                                        reddish-tinged yellow                                                                      PA                          dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-7-methyl-2-methylene-2,3-                                                             p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-5-trifluoromethyl-2-methy-                                                            p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-7-methoxy-2-methylene-2,3-                                                            p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-7-chloro-2-methylene-2,3-                                                             p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-5-chloro-2-methylene-2,3-                                                             p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          dihydroindol-ω-aldehyde                                                  1-Ethyl-3,3-dimethyl-2-methylene-2,3-di-                                                              p-tertiary Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          hydroindol-ω-aldehyde                                                    1-Ethyl-3,3-dimethyl-5-methyl-2-methy-                                                                p-tertiary Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          lene-2,3-dihydroindol-ω-aldehyde                                         1-Ethyl-3,3-dimethyl-5-chloro-2-methyl-                                                               M p-tertiary Butylaniline                                                                      greenish-tinged yellow                                                                     PA                          lene-2,3-dihydroindol-ω-aldehyde                                         1-Ethyl-3,3-dimethyl-5-methoxy-2-methy-                                                               p-tertiary Butylaniline                                                                        yellow      PA                          lene-2,3-dihydroindol-ω-aldehyde                                         1-Ethyl-3,3-dimethyl-5-carboethoxy-2-                                                                 p-tertiary Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1-Ethyl-3,3-dimethyl-5-cyclohexyl-2-                                                                  p-tertiary Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1-Ethyl-3,3-dimethyl-5-benzyl-2-methy-                                                                p-tertiary Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          lene-2,3-dihydroindol-ω-aldehyde                                         1-Ethyl-3,3-dimethyl-5-nitro-2-methy-                                                                 p-tertiary Butylaniline                                                                        reddish-tinged yellow                                                                      PA                          lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-7-benzyl-2-methylene-                                                                 p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          2,3-dihydroindol-ω-aldehyde                                              Mixture of: 1,3,3-Trimethyl-4-methyl-2-                                                               p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    and 1,3,3-trimethyl-6-methyl-2-methy-                                          lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-6,7-benzo-2-methylene-                                                                p-tertiary-Butylaniline                                                                        reddish-tinged yellow                                                                      PA                          2,3,3',4',5',6'-hexahydroindol-ω-                                        aldehyde                                                                       1,3,3-Trimethyl-5-fluoro-2-methylene-                                                                 p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-ethoxy-2-methylene-                                                                 p-tertiary-Butylaniline                                                                        yellow      PA                          2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-7-ethoxy-2-methylene-                                                                 p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-cyano-2-methylene-                                                                  p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-acetylamino-2-methy-                                                                p-tertiary-Butylaniline                                                                        yellow      PA                          lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-5-methylsulphonyl-2-                                                                  p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-5-phenylsulphonyl-2-                                                                  p-tertiary-Butylaniline                                                                        yellow      PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3-Dimethyl-3-ethyl-2-methylene-2,3-                                                                 p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-6,7-benzo-2-methylene-                                                                p-tertiary-Butylaniline                                                                        yellow      PA                          2,3-dihydroindol-ω-aldehyde                                              1,3,3-Trimethyl-5-sulphonamido-2-methy-                                                               p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-5-carbonamido-2-methy-                                                                p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          lene-2,3-dihydroindol-ω-aldehyde                                         1,3,3-Trimethyl-5-carboxylic acid ethyl                                                               p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          anilide-2-methylene-2,3-dihydroindol-                                          ω-aldehyde                                                               1,3,3-Trimethyl-7-ethyl-2-methylene-2,3-                                                              p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-5-chloro-7-methoxy-2-                                                                 p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3-Trimethyl-4-chloro-7-methoxy-2-                                                                 p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω  -aldehyde                                  1,3,3-Trimethyl-4,5-dichloro-7-methoxy-                                                               p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          2-methylene-2,3-dihydroindol-ω-aldehyde                                  1,3,3-Trimethyl-5-chloro-4,7-dimethoxy-                                                               p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          2-methylene-2,3-dihydroindol-ω-aldehyde                                  1,3,3-Trimethyl-4,6-dicarbomethoxy-2-                                                                 p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                    1,3,3,4,5,7-Hexamethyl-2-methylene-2,3-                                                               p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          dihydroindol-ω-aldehyde                                                  1,3,3,4,6,7-Hexamethyl-2-methylene-2,3-                                                               p-tertiary-Butylaniline                                                                        greenish-tinged yellow                                                                     PA                          dihydroindol-ω-aldehyde                                                  1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  3-Amino-phenyl-benzyl-                                                                         greenish-tinged yellow                                                                     PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               ether                                                   1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  2-Amino-phenyl-benzyl-                                                                         greenish-tinged yellow                                                                     PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               ether                                                   1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Aminophenyl-p-methyl-                                                                        greenish-tinged yellow                                                                     PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               benzyl-ether                                            1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  3-Aminophenyl-p-methyl-                                                                        greenish-tinged yellow                                                                     PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               benzyl-ether                                            1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  2-Aminophenyl-p-methyl-                                                                        yellow      PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               benzyl-ether                                            1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Amino-2-methylphenyl-                                                                        yellow      PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               benzyl-ether                                            1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  5-Amino-2-methylphenyl-                                                                        yellow      PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               benzyl-ether                                            1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  2-Amino-5-methylphenyl-                                                                        yellow      PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               benzyl-ether                                            1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Amino-2-methoxyphenyl-                                                                       reddish-tinged yellow                                                                      PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               benzyl-ether                                            1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Amino-3-methoxyphenyl-                                                                       yellow      PA                          butyl-2,3-dihydroindol-ω  -aldehyde                                                             benzyl-ether                                            1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Amino-3-methylphenyl-                                                                        yellow      PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               benzyl-ether                                            1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Amino-4'-cyclohexyl-                                                                         yellow      PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               diphenyl-ether                                          1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Amino-2'-methyl-diphenyl-                                                                    yellow      PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               ether                                                   1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Amino-3'-methyl-diphenyl-                                                                    yellow      PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               ether                                                   1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Amino-4'-methoxy-diphenyl-                                                                   greenish-tinged yellow                                                                     PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               ether                                                   1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Amino-3'-methoxy-                                                                            yellow      PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               diphenyl-ether                                          1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Amino-4'-ethoxy-diphenyl-                                                                    yellow      PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               ether                                                   1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Amino-4'-acetylamino-                                                                        yellow      PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               diphenyl-ether                                          1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Amino-4'-hydroxy-                                                                            yellow      PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               diphenyl-ether                                          1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Aminophenyl-α-                                                                         greenish-tinged yellow                                                                     PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               naphthyl-ether                                          1,3,3-Trimethyl-2-methylene-5-tert.-                                                                  4-Aminophenyl-β-                                                                          greenish-tinged yellow                                                                     PA                          butyl-2,3-dihydroindol-ω-aldehyde                                                               naphthyl-ether                                          1,3,3-Trimethyl-2-methylene-5-tert.-                                           5'-                    4-Amino-2', -3'                                                                yellow          PA                                      butyl-2,3-dihydroindol-ω-aldehyde                                                               trimethyldiphenyl-                                                             ether                                                   1,3,3-Trimethyl-7-phenoxy-2-methy-                                                                    p-tertiary-Butylanil-                                                                          greenish-tinged yellow                                                                     PA                          lene-2,3-dihydroindol-ω-aldehyde                                                                ine                                                     1,3,3-Trimethyl-7-benzyloxy-2-                                                                        p-tertiary-Butyl-                                                                              greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-aldehyde                                                           aniline                                                 1,3,3-Trimethyl-5-phenoxy-2-methy-                                                                    p-tertiary-Butyl-                                                                              greenish-tinged yellow                                                                     PA                          lene-2,3-dihydroindol-ω-aldehyde                                                                aniline                                                 1,3,3-Trimethyl-5-benzyloxy-2-methy-                                                                  p-tertiary-Butyl-                                                                              greenish-tinged yellow                                                                     PA                          lene-2,3-dihydroindol-ω-aldehyde                                                                aniline                                                 1,3,3-Trimethyl-5-carbobenzoxy-2-                                                                     p-tertiary-Butyl-                                                                              greenish-tinged yellow                                                                     PA                          methylene-2,3-dihydroindol-ω-                                                                   aniline                                                 aldehyde                                                                       __________________________________________________________________________

EXAMPLE 3

Dyeing is carried out as described in Example 1, but instead of the dyestuff described there the same amount of the dyestuff of the formula ##STR8## is used. A bluish-tinged red dyeing of uniform strength and excellent wet fastness propertie is obtained.

The dyestuff had been obtained as follows: 7 parts of 1,3,3-trimethyl-5-tertiary butyl-2-methylene-2,3-dihydroindole and 5.5 parts of 4-dimethylamino-benzaldehyde in 15 parts by volume of glacial acetic acid were stirred for 3 hours at 100° C. The dyestuff melt was then poured into 300 parts of water and the dyestuff was salted out with 20 parts of sodium chloride, separated from the solution and dried.

Equivalent dyeings, in the colour shades indicated in the table, were also obtained on polyacrylonitrile textile materials if instead of the dyestuff used the same amount of one of the dyestuffs obtained on reaction of 1,3,3-trimethyl-5tert.-butyl-2-methylene-2,3-dihydroindole with the aldehydes indicated in the table was employed.

                  Table                                                            ______________________________________                                         Aldehyde                  Colour shade                                         ______________________________________                                         p-Dimethylamino-benzaldehyde                                                                            bluish-tinged                                                                  red                                                   p(2-Chloroethyl-butyl-amino)-benzaldehyde                                                               red-violet                                            N-methyl-p-ethoxy-diphenylamine-(4)-aldehyde                                                            reddish-tinged                                                                 violet                                                N-ethylcarbazolaldehyde  orange                                                1-Methyl-2-phenylindol-3-aldehyde                                                                       orange                                                1-Methyl-2-phenyl-5-tertiary butyl-indol-3-                                    aldehyde                 orange                                                ______________________________________                                    

Equivalent dyeings, in the colour shades indicated in the table, were also obtained on anionically modified polyacrylonitrile if instead of the dyestuff employed the same amount of one of the dyestuffs obtained on reaction of the aldehydes and dihydroindoles listed in the table, under the manufacturing condition described for the dyestuff used, was employed.

                  Table                                                            ______________________________________                                                                          Colour                                        Aldehyde     Dihydroindole       shade                                         ______________________________________                                         1-Methyl-2-phenyl-                                                                          1,3,3-trimethyl-5-n-butyloxy-                                                                      orange                                        indol-3-aldehyde                                                                            2-methylene-2,3-dihydroindole                                     1-n-Butyl-2-phenyl-                                                                         1,3,3-trimethyl-5-tertiary                                                                         orange                                        indol-3-aldehyde                                                                            butyl-2-methylene-2,3-dihydro-                                                 indole                                                            1-Isobutyl-2-phenyl-                                                                        1,3,3-trimethyl-5-tertiary                                                                         orange                                        indol-3-aldehyde                                                                            butyl-2-methylene-2,3-dihydro-                                                 indole                                                            ______________________________________                                    

EXAMPLE 4

A fabric of anionically modified polyester fibres (Dacron 64) is dyed, in accordance with the procedure indicated in Example 1, in a bath which per liter of tetrachloroethylene contains 1 g of the dyestuff of the formula ##STR9## 1 g of oleic acid ethanolamide, 1 g of the reaction product of 1 mol of oleyl alcohol with 20 mols of ethylene oxide, 8 g of water and 1 g of glacial acetic acid.

A uniform green dyeing of good wet fastness properties is obtained.

The dyestuff had been manufactured as follows: 15 parts of 4-diethylamino-4'-tert.-butyl-benzophenone, 11 parts of N-methyl-p-ethoxydiphenylamine and 30 parts of phosphorous oxychloride were stirred, 10 parts of phosphorus pentoxide were then added and the mixture was heated to 100° C. for 2 hours. The melt was introduced into 500 parts of water, and stirred therein until the phosphorus oxychloride was decomposed. After adding 30 parts of sodium chloride, the dyestuff was filtered off.

If instead of 4-diethylamino-4'-tert.-butyl-benzophenone the equivalent amount of 4-phenylmethylamino-5-tertiary butylbenzophenone was employed, a dyestuff was obtained with which an even yellowish-tinged green dyeing also having excellent fastness properties was obtained.

EXAMPLE 5

A fabric of polyacrylonitrile fibres is dyed in accordance with the procedure described in Example 1 with the dyestuff of the formula ##STR10## A uniform, blue-green dyeing of good fastness properties is obtained.

The dyestuff had been manufactured as follows: 15 parts of 4-tert.-butyl-4'-diethylamino-benzophenone, 10 parts of 1-methyl-2-phenylindole and 30 parts of phosphours oxychloride were stirred for 4 hours at 100° C. The melt was then poured into 400 parts of water and stirred until the phosphorus oxychloride was decomposed. After adding 20 parts of sodium chloride, the dyestuff was filtered off and dried.

Equivalent dyeings in the colour shades indicated in the table, on the substrates indicated in the table, were also obtained if instead of the dyestuff used the same amount of one of the dyestuffs obtained on reaction of the benzophenones and indoles indicated in the table, under the manufacturing conditions described for the dyestuff used, was employed (PA = anionically modified polyacrylonitrile, PE = anionically modified polyester).

                                      Table                                        __________________________________________________________________________       Benzophenone      Indole         Colour shade                                                                             Substrate                         __________________________________________________________________________     4-Diethylamino-4-tertiary-butyl-                                                                  1,2-Dimethylindole                                                                             strongly reddish-                                                                        PA                                benzophenone                       tinged blue                                 4-Di-n-propylamino-4-tertiary                                                                     1,2-Dimethylindole                                                                             reddish-tinged                                                                           PE                                butyl-benzophenone                 blue-grey                                   4-Di-n-propylamino-4-tertiary                                                                     1-Methyl-2-phenylindole                                                                        bluish-tinged                                                                            PE                                butyl-benzophenone                 grey-green                                  4-N-phenyl-N-methylamino-4-                                                                       1,2-Dimethylindole                                                                             reddish-tinged                                                                           PE                                tertiary butyl-benzophenone        grey-blue                                   4-N-phenyl-N-methylamino-4-                                                                       1 Methyl-2-phenylindole                                                                        green     PE                                tertiary butyl-benzophenone                                                    4-Diethylaminobenzophenone                                                                        1-Ethyl-2-phenyl-5-tertiary                                                                    greenish-tinged                                                                          PE                                                   butylindole     blue                                        4-Diethylamino-2-chlorobenzo-                                                                     1-Ethyl-2-phenyl-5-tertiary                                                                    greenish-tinged                                                                          PE                                phenone            butylindole     blue                                        4-Phenylmethylamino-benzophenone                                                                  1-Ethyl-2-phenyl-t-tertiary-                                                                   blue-green                                                                               PE                                                   butylindole                                                 4-Diethylamino-benzophenone                                                                       1-Dodecyl-2-phenylindole                                                                       blue-grey PE                                4,4'-Bis-diethylaminobenzo-                                                                       1-Dodecyl-2-phenylindole                                                                       reddish-tinged                                                                           PE                                phenone                            blue                                        4-Dimethylamino-4'-tertiary                                                                       1,2-Dimethylindole                                                                             strongly reddish-                                                                        PA                                butyl-benzophenone                 tinged blue                                 4-Dimethylamino-4'-tertiary                                                                       1-Methyl-2-phenylindole                                                                        greenish-tinged                                                                          PA                                butyl-benzophenone                 blue                                        4-Diethylamino-4'-methoxy-                                                                        1-Ethyl-2-phenyl-5-tert.-                                                                      black-grey                                                                               PE                                benzophenone       butylindole                                                 4-Dimethylamino-4'-methoxy-                                                                       1-Ethyl-2-phenyl-5-tert.-                                                                      reddish-tinged                                                                           PA                                benzophenone       butylindole     grey                                        4-N(p-Ethoxy-phenyl)N-methylamino-                                                                1-Ethyl-2-phenyl-5-tert.-                                                                      green     PE                                benzophenone       butylindole                                                 4-Aminobenzophenone                                                                               1-Ethyl-2-phenyl-5-tert.-                                                                      bluish-tinged red                                                                        PA                                                   butylindole                                                 4-Aminobenzophenone                                                                               1-Dodecyl-2-phenylindole                                                                       claret    PE                                __________________________________________________________________________

EXAMPLE 5

Polyacrylonitrile fibre yarn is dyed in accordance with the procedure indicated in Example 1 with the dyestuff of the formula ##STR11## A bluish-tinged red dyeing of good wet fastness properties is obtained.

The dyestuff had been obtained by heating equimolar amounts of 1,3,3-trimethyl-5-t.-butyl-2-methylene-2,3-dihydroindol-ω-aldehyde and 1,3,3-trimethyl-2-methylene-2,3-dihydroindole, in the same amount by weight of a mixture of 75% of glacial acetic acid and 25% of acetic anhydride, to 100° C. for 5 hours, subsequently stirring the mixtue with a 20-fold amount of water, and salting out with sodium chloride.

Equivalent dyeings, in the colour shades indicated in the table, were also obtaned if instead of the dyestuff used the same amount of one of the dyestuffs which are obtained in the reaction of the dihydroindoles indicated in the table with 1,3,3-trimethyl-5-tert.-butyl-2-methylene-2,3-dihydroindol-ω-aldehyde, under the manufacturing conditions described for the dyestuff used, was employed.

                                      Table                                        __________________________________________________________________________            Dihydroindole             Colour shade                                  __________________________________________________________________________     1,3,3-Trimethyl-2-methylene-5-methoxy-ω-cyano-2,3-dihydroindole                                          bluish-tinged red                              1,3,3-Trimethyl-2-methylene-5-chloro-2,3-dihydroindole                                                         bluish-tinged pink                             1,3,3-Trimethyl-2-methylene-5-methyl-2,3-dihydroindole                                                         bluish-tinged red                              1,3,3-Trimethyl-2-methylene-5-cyano-2,3-dihydroindole                                                          bluish-tinged pink                             1,3,3-Trimethyl-2-methylene-5-carbomethoxy-2,3-dihydroindole                                                   bluish-tinged pink                             1,3,3-Trimethyl-2-methylene-5-methoxy-2,3-dihydroindole                                                        bluish-tinged red                              1,3,3-Trimethyl-2-methylene-7-methyl-2,3-dihydroindole                                                         bluish-tinged red                              1,3,3-Trimethyl-2-methylene-7-chloro-2,3-dihydroindole                                                         bluish-tinged pink                             1,3,3-Trimethyl-2-methylene-5-tert.-butyl-2,3-dihydroindole                                                    bluish-tinged red                              1,3,3-Trimethyl-2-methylene-5-methyl-sulphonyl-2,3-dihydroindole                                               bluish-tinged pink                             1,3,3-Trimethyl-2-methylene-5-nitro-2,3-dihydroindole                                                          strongly bluish-tinged red                     __________________________________________________________________________ 

I claim:
 1. In the process of dyeing an anionically modified fiber material by exhaustion from a dyebath consisting essentially of a cationic dyestuff dissolved in halogenated hydrocarbon the improvement comprising the use as said cationic dyestuff a dyestuff soluble in said halogenated hydrocarbon and having the formula ##STR12## in which A⁻ is a non-lipophilic anion;R₁₂ is hydrogen, alkyl, aralkkyl, cycloalkyl or aryl; R₁₃ is hydrogen, alkyl, cycloalkyl or aralkyl, or R₁₂ and R₁₃ together with the nitrogen atom form a heterocyclic ring which can contain further hetero-atoms; R₁₄ is hydrogen, halogen, alkoxy, aralkoxy, aryloxy, acyloxy, alkyl, aralkyl, aryl, nitro, CN, trifluoromethyl, carboxylic acid ester, carbonamide, N-substituted carbonamide, acyl, alkysulphonyl or arylsulphonyl or ##STR13## in which R₉ is hydrogen, alkyl, alkoxy or halogen; R₁₀ is hydrogen, alkyl, aralkyl, cycloalkyl or aryl; R₁₁ is alkyl, aryl, carboxylic acid ester, carbonamide or substituted carbonamide; R₁₅ is hydrogen, alkyl, cycloalkyl or aralkyl; R₁₆ is hydrogen, alkyl, aralkyl, cycloalkyl or aryl; or R₁₅ and R₁₆, together with the nitrogen atom, form a heterocyclic ring which can contain further hetero-atoms; R₁₇ is hydrogen, halogen, alkyl or alkoxy, and in which the aromatic carbocyclic rings of the dyestuff cation can be condensed with carbocyclic rings and additionally the substituents R₉, R₁₄ and R₁₇ can contan further non-ionic substituents;with the proviso that at least one of the substituents R₉, R₁₁, R₁₄ or R₁₇ is a C₃ -C₁₃ -alkyl, C₃ -C₁₂ -alkoxy or C₅ -C₆ -cycloalkyl group or R₁₀ is a C₃ -C₁₂ -alkyl or C₅ -C₆ -cycloalkyl group.
 2. Process according to claim 1 in which said dyebath also contains 0.1 to 4 percent by weight of water relative to the weight of the halogenated hydrocarbon.
 3. Process of claim 1 in which said non-lipophilic anion is chloride, bromide, iodide, carbonate, bicarbonate, sulphate, bisulphate, disulphate, aminosulphonate, phosphate, dihydrogenophosphate, nitrate, perchlorate, ZnCl₃.sup.⁻, p-chlorobenzenesulphonate, methylsulphate, ethylsulphate or the anion of formic acid, acetic acid, chloroacetic acid, propionic acid, lactic acid, crotonic acid, benzoic acid, oxalic acid, malonic acid, maleic acid, citric acid, tartaric acid, succinic acid, adipic acid or suberic acid. 